O,S,N-tri-aliphatic hydrocarbon-thionothiolphosphoric acid ester amides

ABSTRACT

O,S,N-tri-aliphatic hydrocarbon-thionothiolphosphoric acid ester amides of the general formula   in which R, R1 and R2, which may be the same or different, each is an alkyl, alkenyl or alkynyl radical with up to 6 carbon atoms, optionally substituted with at least one halo, phenyl, cyano, alkoxy, alkylmercapto, phenylmercapto or naphthylmercapto radical, the mercapto radicals being optionally chloro- or cyano-substituted, WHICH POSSESS NEMATOCIDAL, INSECTICIDAL, ACARIDICAL, FUNGICIDAL AND MAMMALIAN-REPELLENT PROPERTIES.

United States Patent Stolzer et a1. Sept. 2, 1975 [54] O,S,N-TR1-ALIPHAT1C 3,787,539 1/1974 Colln et a1. 260/959 HYDROCARBON-THIONOTHIOLPl-IOS- PHORIC ACID ESTER AMIDES Inventors: Claus Stiilzer,

Wuppertal-Vohwinkel; Bernhard Homeyer, Opladen; Ingeborg Hammann, Cologne; Giinter Unterstenhiifer, Opladen, all of Germany Bayer Aktiengesellschaft, Leverkusen, Germany Filed: Nov. 8, 1973 Appl. No.: 414,601

Related US. Application Data Division of Ser. No. 160,185, July 6, 1971, Pat. No. 3,793,407.

Assignee:

OTHER PUBLICATIONS Mandelbaum et al., Chemical Abstracts, Vol. 66, (1967).

Primary Examiner-Richard L. Raymond Attorney, Agent, or FirmBurgess, Dinklage & Sprung [57] ABSTRACT O,S,N-tri-aliphatic hydrocarbon-thionothiolphosphoric acid ester amides of the general formula in which R, R and R, which may be the same or different,

each is an alkyl, alkenyl or alkynyl radical with up to 6 carbon atoms, optionally substituted with at least one halo, phenyl, cyano, alkoxy, alkylmercapto, phenylmercapto or naphthylrnercapto radical, the mercapto radicals being optionally chloroor cyano-substituted,

which possess nematocidal, insecticidal, acaridical,

fungicidal and mammalian-repellent properties.

3 Claims, No Drawings O,S,N-TRI-ALIPHATIC HYDROCARBON-THIONOTHIOLPHOSPHORIC ACID ESTER AMIDES This is a divsion of application Ser. No. 160,185, filed July 6, 1971 now US. Pat. No. 3,793,407.

The present invention relates to and has for its objects the provision of particular new O,S,N-tri-aliphatic hydrocarbonthionothiolphosphoric acid ester amides, i.e. 0,5, and N-(mono)alkyl, alkenyl or alkynyl-thionothiolphosphoric acid ester amides, Whichpossess nematocidal, insecticidal, acaricidal, fungicidal and mammalian-repellent properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. nematodes, insects, acarids, fungi and destructive mammals, especially nematodes, insects and acarids, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from German Published Specification No. 1,032,247 and German Patent Specification Nos. 830,509 and 917,668 that certain 0,0,S-trialkylthionophosphoric acid esters, for example the 0,0- diethyl-S-2-ethylmercaptoethyl ester of thionothiophosphoric acid (Compound A), possess insecticidal and acaricidal properties.

The present invention provides, as new compounds, the O-alkyl (alkenyl, alkynyl)-S-alkyl(alkenyl,alkynyl)- N-monoalkyl(alkenyl,alkynyl)-thionothiolphosphoric acid ester amides of the general formula ROS in which R, R and R which may be the same or different, each is an alkyl, alkcnyl or alkynyl radical with up to 6 carbon atoms, optionally substituted with at least one halo, phenyl, cyano, alkoxy, alkylmercapto, phenylmercapto or naphthylmercapto radi cal, the mercapto radicals being optionally chloroor cyanosubstituted.

The compounds of the formula (I) have been found to exhibit good insecticidal and acaricidal activity and a particularly strong nematocidal activity, as well as also exhibiting fungicidal activity and a repellent action towards destructive mammals.

The present invention also provides a process for the preparation ofa compound of the formula (I), in which an O-alkyl(alkenyl, alkynyl)-N-monoalkyl(alkenyl, alkynyl) amino-thionothiolphosphoric acid ester salt of the general formula ROS PSM (ll) in which I R and R have the meanings stated above, and

M stands for an alkali metal equivalent, an alkaline earth metal equivalent or an optionally alkylsubstituted ammonium equivalent, is reacted with a compound of the general formula Hal-R in which R has the meaning stated above, and

Hal stands for a halogen atom, preferably a chlorine or bromine atom.- i

Surprisingly, the novel thionothiolphosphorie acid ester amides of the general formula (I) possess not only very good insecticidal and acaricidal properties, but also a considerably higher nematocidal activity than the known 0,0,S-trialkyl-phosphoric acid esters which are chemically the most closely comparable compounds of the same type of activity. The compounds of the invention are therefore an enrichment of the art.

If the potassium salt of O-ethyl-N- monoisopropylthionothiolphosphoric acid ester amide and l-chloro-2-ethyl-mercaptoethane are used as starting materials, the reaction may be represented by the following equation:

Preferably, R and R each stands for a straight or branched-chain alkyl radical with l4 carbon atoms or an alkenyl radical with 24 carbon atoms, for example for methyl, ethyl nor isopropyl, n-, iso-, sec.- or tert.-

butyl or allyl. R stands preferably for a straight-chain or branched alkyl radical with 1-4 carbon atoms or for allyl, methallyl or propargyl. Further preferred meanings for R, R? and R especially R are straight or branched-chain alkyl groups with 1-4 carbon atoms and alkenyl groups with 2-4 carbon atoms, which alkyl and alkenyl groups each carry at least one substituent selected from the group consisting of chlorine and bromine atoms and cyano, lower alkoxy, lower alkylmercapto, phenylmercapto and naphthylmercapto radicals, the said mercapto radicals being optionally chloroor cyano-substituted. The preferred cyclic alkyl radical is eyclohexyl. V i

As examples of the starting materials of the formula (II); there may be mentioned the potassium, sodium and ammonium salts of the O-methyl-N-rn ethyl, O- methyl-N-ethyl, Q-methylN-isopropylg O-mcthyI-N npropyl, O methyl-N-(m, iso-, sec or tert.-)butyl, O-ethylN-methyl O-ethyl-n-ethyl-, Octhyl-N- npropyl-, O-ethyl-N-isopropyl-, O ethyl-N(n-, iso-, sec.- or tert.)butyl-, O-n-propylNmethyl-, O-npropyl-N- ethyl-, On-propyl-N-n-propyl O-n-propyl-N- isopropyl, O-n-propyl-N-(m, iso-, sec or tert.-) butyl-, O isopropyl-N-rnethyl-, O-isopropyl-N-ethyl O-isopropyl-N-n-propyl-, O-isopropyl-N-isopropyl-, O-isopropyl-N-(n-, iso-, sec.- or tert.-) butyl-, O-(n,

iso-, sec.- or tert.-)butyl-N-methyl-, O-(n-, iso-i, sec.-'or tert.-)butyl-N-ethyl and O-(n-, iso-, sec.- or tert- )butyl-N-isopropyl-thionothiolphosphoric acid ester possibly chlorinated hydrocarbons, such as benzene.

toluene, xylenes, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; others, such as diethyl ether, dibutyl ether and dioxane; ketones, such as acetone and. mcthylethyl, methylisopropyl and methylisobutyl ketones; nitriles, such as acetonitrile; and alcohols, such as methanol, ethanol and propanol. In some cases also water may be used as solvent or diluent. The reaction temperatures can be varied within a fairly wide range: in general, the reaction is effected at about to 100C, preferably about 30 to 40C.

The reaction is, in general, carried out at normal pressure.

When carrying out the process of the invention, the salts of the formula (II) and the halogen compounds of the formula (III) are, in most cases, used in equimolar amounts. An excess of one or the other of the reactants brings no substantial advantages. Preferably, the reaction is effected in one of the above-mentioned solvents at about 30 to 40C; the reaction mixture is thereafter stirred for some hours and worked up according to any customary method.

The substances according to the invention are obtained in most cases in the form of colorless to slightly yellow-cored, viscous, water-insoluble oils which in many cases cannot be distilled without decomposition but which can, by so-called slight distillation, that is by longer heating to moderately elevated temperature under reduced pressure, be freed from the last volatile components and in this way be purified. For their characterization, the refractive index is especially suitable; Solid compounds are characterized by their melting points. As already mentioned, the compounds according to the invention are characterized by outstanding nematocidal, insecticidal and acaricidal properties. They possess at the same time a good effectiveness against both sucking and biting insects. Dipteria, mites, as well as a systemic activity. In addition, they also show a fungitoxie effectiveness against phytopathogenie fungi, for example Piricularia oryzae, as well as a repellent action twoards destructive mammals. The products, therefore, may be used with success in crop protection and the protection of stored products, as well as in the hygiene field, against the most diverse animal pests.

To the sucking insects contemplated herein there belong, in the main, aphids (Aphidae) such as the green peach aphid (ll/lyzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rlmpalosiphum padi the pea aphid (Macrosiphum pisi) and the potato aphid (Maerosiphum solariifrflii), the rosy apple aphid (Sappaphis mall), the mealy plum aphid (Hyalopterus arundinis), the currant gall aphid (Cryptomyzus korsclzelti), and the cherry blackfly (Myzils eerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecanium hesperidum) as well as the grape mealybug (Pseudocoecus maritimus); thrips (Thysanoprera), such as Hereirwt/zripsfemm'alis, and bugs, for example the beet bug (Plasma quadram), the red cotton bug (Dysclereus intermedl'us), the bed bug (Cimex Iecrularius), the assassin bug (Rlzodnius prolixus) and Chagas bug (Trfamma infestans) and, further, cicadas, such as Euscelis bilobatus and Nep/mtettix bipunc tatus; and the like.

in the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptefa) such as the daimond-back moth (Plutella maculipennis), the gypsy moth (Lyman l ria dispar), the brown-tailed moth (Euproctis chrysurrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agmtis seg mm), the large white butterfly (Pieris brassicae), the small winter moth (Cheimzitobia brumata), the green oak tortrix moth, (T( )rrrix viridana), the fall armyworm (Laphygma frugiperda) and cotton work (Prozlenia litura) the ermine moth I (Hyponomeuta padella), the Mediterranean flour moth (Ephestia killiniella) and greater wax moth (Galleria mellunella); and the like.

Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary weevil (Sitop/zilus granarius Cala'ndra granaria), the Colorado beetle (Leptinomfsa decemlineata), the dock beetle (Gastruplzysa viridula), the mustard beetle (Phaedon cuchleariae), the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturus mnzentosus), the bean weevil (Bruchidius Aeanthoscelides obtectus), the leather beetle (Dermestesfrischi), the khapra beetle (Trogoderma granarium), the flour beetle (Tribolium Castaneum), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio mulitor) and the saw-toothed grain beetle (Oryzaephilus surinamensis), and also species living in the soil, for example Wireworms (Agriotes spec.) and larvae of the c'oekcliafer (Melolontha melolontha); cockroaches, such as the German cockroach (Blattella germanica), American cockroach (Periplaneta americana), Madeira cockroach (Leuco'phaea or Rhyparaboia maderae), oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta; further, Orthoptera. for example the house cricket (Acheta domes'ticus); termites such as the eastern subterranean termite (Retieulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (C eratitis capitata), the house fly (MUSCG domestica), the little house fly (Fann'ia canicularis) the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythrueephala) as well as the stable fly (Smmoxys.ealcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Ac-arina) contemplated herein there are classed, in particular, the spider mites (Tetranyclzia'ae) such as the two-spotted spider mite (Telrany- (has telarius Tetranyclzus althueae or Tetranyclms urticae) and the European red mite (Paratetranychus pilosus Panonychus' ulmi), gall mites, for example the black current gall mite (hriopliyes rz'bis) and mrsmw' mia'x. for example the broad mite (Hamimrsmmm" [w ms) and the Cyclamen mite (Tm'sonenzus pallidus); finally, ticks, such the relapsing fever tick (Ornir/mzlorus muuham); and the like.

When applied against pests harmful to health and pests of stored products, especially flies and mosquitoes, the compounds of the invention are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispcrsible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispcrsible liquid diluent carriers and/or dispcrsible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispcrsible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (c.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraffins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc. alcohols (e.g. metahnol, ethanol, propanol, butanol, etc), amines (e.g. ethanolaminc, etc.), ethers, ether-alcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sufloxides (c.g. dimethyl sufloxide, etc.), ketones (e.g. acetone, etc.), and/or water; as well as inert dispcrsible finely divided solid carriers, such as ground natural minerals (c.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g., highly dispersed silicic acid, silicates e.g. alkali silicates, etc. whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispcrsible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides, insec' ticides, fungicides, bacterieides and nematocides, or rodcnticides, herbicides, fertilizers, growth-regulating agents, etc., if desired, or in the form' of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight and preferably O.5-7c by weight, of the mixture, whereas carrier composition mix-tures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.000140%, preferably 001-171, by weight of the mixture. Thus the present invention contemplates over-all compositions which comprise mixtures of a conventional dispcrsible carrier vehicle such as l a dispcrsible inert finely divided carrier solid, and/or (2) a dispcrsible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, and an amount of the active compound which is effective for the purpose in question and which is generally be tween about 0.0001-7z, and preferably 0.0l95 /z, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. in mist form, for example by airplane crop straying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 15 to 1000 g/hectare, preferably 40 to 600 g/hectarc, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound or even the active substance alone, eg about 20l00% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. nematodes, insects, acarids, fungi and de structive mammals and more particularly methods of combating at lease one of nematodes, insects and acaricls which comprises applying to at least one of correspondingly (a) such nematodes, (b) such insects, (e) such acarids, (d) such fungi and (f) the corresponding habitat thereof or of destructive mammalian pests, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. a nematociclally, insccticidally, acaricidally, fungicidally, or mammalian-repellent effective amount of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehiclewill depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration of the particular new compounds of the presentinvehtion are illustrated, without limitation, by the following examples:

EXAMPLE 1 Myzus test (contact action) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the EXAMPLE 2 Tetranychus test Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether Table 1 Active compounds (Myzus test) Concentration of active compound Degree of destruction stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

To produce a-suitable preparation of active com- .pound, l part by weight of the active compound is Cabbage plants (Brassicu olerucea) which have been 65 mixed with the stated amountof solvent containing the heavily infested with peach aphids (Myzus persicue) are sprayed with the prc'parationofi-the active-compound until dripping wet.

stated amountof emulsifier and the concentrate so obtained is diluted with water to the desired concentration.

Bean plants (Plum-(0111s vulgar-is), which have a height of approximately l-30 cm., are sprayed with the preparation of the active compound until dripping wet. These bean plants are heavily infested with spider mites (Tetrmrvchus urticae) in all stages of development.

After the specified periods of time, the effectiveness of the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: 100% means that all the'spider mites are killed whereas 0% means that none of thespider mites are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 2:

Table 2 pound, 1 banby weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with (Tetranyehus test) Active compounds Concentrations of active compound Degree of destruction in 7r Solvent: 3 parts by weight acetone, I Emulsifier: l part by weight alkylarylpolyglycol ether To produce a suitable preparation of active comin /1 by weight after 2 days 5 ll C t-1,7,0 .PSCH2-CH- ,S-CH. ,CH:, 0.1 95

0.01 0 (known) (A) C. .H,-,O\S II P-s-cH s c 1t, o. 1 100 CH -,--NH/ 0.01 100 35 C ,H ,0\s ll SCH -CH Cl 0.1 99 (CH,,)2CH-NH 0.01 98 C2H -,O\S ll /P-S-CH -S -C H,, 0. 1 100 (CH:,)2CH-NH 0.01 90 5) C2H -,O\S CH. .C1

II I /PSCH.,SCCN 0. 1 100 (211 )2CHNH CH 0.01

C. .H -,0\s

,Il ,/PS-CH .CH S-C H 0.1 100 (CH,'.). .CH7NH 0.01 100 H I (l) EXA L compound is determined as a percentage. The degree V of effectiveness is 100% when infestation is completely criticaltcncemmtion test avoided; itis .O% when the infestation is exactly the T t d M l sameas inthe case of the control plants in untreated cbt O e 01 ogync soil which .has been infested in the same manner.

The active compounds, the amounts applied and the results can be seen from the following Table 3:

Table 3 (Nvmumrizluv i't lvluialqqvm' im ugnim) Degrcc of destruction in 9! with a concentration of active Active compound compound in ppm of (known) (A) The following examples will illustrate the compounds of the invention.

EXAMPLE 4 To 97.2 g 0.44 mole) of the sodium salt of O-cthyl- N-monoisopropylthionothiolphosphoric acid ester amide in 300 cc of acetonitrile there are added slowly,

at 40, 49.8 g (0.4 mole) of l-chloro-2-ethyl-rnercaptoethane. The mixture is afterwards stirred over-night at 40C; it is poured into water; the mixture is taken up in benzene; the organic phase is washedneutralwith-wa- Analogously, thefollowin g' compounds are prepared:

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

l. A thionothiolphosphoric acid ester amide of the formula in which R and R each is an'alkyl, alkenyl or alkynyl radical with up to 6 carbon atoms, optionally substituted UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3 ,903 ,209 DATED September 2, 1975 INVIENTOR (S) Claus Stolzer et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 34, insert I "KCL at the beginning of Compound IV in the equation.

Column 5, 1ine 39, correct spelling of "methanol".

Column 5, line 44, correct spelling of "sulfoxides".

Column 8, line 60, correct Compound 9 to read as follows:

C1 C-CH -O S P-S-CHZ-CHZ-S-CZHS 14 11 -1111 Signed and Scaled this Sixth Day of July 1976 [SEAL] Arrest:

RUTH C. MASON Arresting Officer 

1. ATHIONOTHIOLPHOSPHORIC ACID ESTER AMIDE OF THE FORMULA
 2. A compound according to claim 1 in which R and R1 is alkyl with up to 4 carbon atoms, and R2 is alkyl of up to 4 carbon atoms carrying at least one chloro or bromo.
 3. Compound according to claim 1 wherein such compound is O-ethyl-S-(2-chloroethyl)-N-isopropyl-thionothiolphosphoric acid ester amide of the formula 